Diallyl dichloroacetmide herbicide antidote

ABSTRACT

An herbicide antidote composition comprising: 
     (a) an herbicidally effective amount of a pyrrolidone compound of the formula ##STR1##  in which X is hydrogen, chlorine or methyl; 
     Y is hydrogen, chlorine, or bromine; 
     Z is chlorine or bromine; 
     R is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, or 3-methylureido; 
     R 1  is hydrogen, alkyl, chlorine, or trifluoromethyl; and, 
     R 2  is alkyl or hydrogen; and, 
     (b) a non-phytotoxic antidotally effective amount of a compound of the formula ##STR2##

FIELD OF THE INVENTION

This invention relates to herbicide antidotes, and, more particularly,to diallyl dichloroacetamide, which is useful as an herbicide antidote.

BACKGROUND OF THE INVENTION

An herbicide is a compound which adversely controls or modifies plantgrowth, e.g., killing, retarding, defoliating, desiccating, regulating,stunting, tillering, stimulating, and dwarfing. The term "plant" refersto all physical parts of a plant, including seeds, seedlings, saplings,roots, tubers, stems, stalks, foliage, and fruits. "Plant growth"includes all phases of development from seed germination to natural orinduced cessation of life.

Herbicides are generally used to control or eradicate weed pests. Theyhave gained a high degree of commercial success because it has beenshown that such control can increase crop yield and reduce harvestingcosts.

The most popular methods of herbicide application include: pre-plantincorporation into the soil; in-furrow application to seeds andsurrounding soil; pre-emergence surface treatment of seeded soil; andpost-emergence treatment of the plant and soil.

A manufacturer of an herbicide generally recommends a range ofapplication rates and concentrations calculated to maximize weedcontrol. The range of rates varies from approximately 0.01 to 50 poundsper acre (0.0112 to 56 kilograms per hectare (k/ha)), and is usually inthe range of from 0.1 to 25 pounds per acre (0.112 to 28 k/ha). The term"herbicidally effective amount" describes the amount of an herbicidecompound which controls or modifies plant growth. The actual amount useddepends upon several considerations, including particular weedsusceptibility and overall cost limitations.

The most important factor influencing the usefulness of a givenherbicide is its selectivity towards crops. In some cases, a beneficialcrop is susceptible to the effects of the herbicide. In addition,certain herbicidal compounds are phytotoxic to some weed species but notto others. To be effective, an herbicide must cause minimal damage(preferably no damage) to the beneficial crop while maximizing damage toweed species which plague that crop.

To preserve the beneficial aspects of herbicide use and to minimize cropdamage, many herbicide antidotes have been prepared. These antidotesreduce or eliminate damage to the crop without substantially impairingthe damaging effect of the herbicide on weed species; See, for example,U.S. Pat. Nos. 4,021,224 and 4,021,229 and Belgian Pat. No. 846,894.

The precise mechanism by which an antidote reduces herbicidal cropinjury has not been established. An antidote compound may be a remedy,interferent, protectant, or antagonist. As used herein, "antidote"describes a compound which has the effect of establishing herbicideselectivity, i.e., continued herbicidal phytotoxicity to weed speciesand reduced or non-phytotoxicity to cultivated crop species. The term"antidotally effective amount" describes the amount of an antidotecompound which counteracts a phytotoxic response of a beneficial crop toan herbicide.

DESCRIPTION OF THE INVENTION

It has now been discovered that diallyl dichloroacetamide is aneffective antidote for the protection of corn crops from pyrrolidoneherbicide injury. This compound has the following formula: ##STR3##

This invention embodies a two-part herbicidal system comprised of:

(a) an herbicidally effective amount of a pyrrolidone compound of theformula ##STR4## in which X is hydrogen, chlorine or methyl;

Y is hydrogen, chlorine, or bromine;

Z is chlorine or bromine;

R is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine,trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl,trifluoromethylsulfonyl, pentafluoropropionamido, or 3-methylureido;

R₁ is hydrogen, alkyl, chlorine, or trifluoromethyl; and,

R₂ is alkyl or hydrogen; and,

(b) a non-phytotoxic antidotally effective amount of a compound of theformula ##STR5##

In a preferred embodiment, X is hydrogen, Y is chlorine, Z is chlorine,R is m-trifluoromethyl, R₁ is hydrogen and R₂ is hydrogen.

This invention also includes the method of establishing herbicidalselectivity which comprises applying to the locus where selectivity isdesired a composition comprising

(a) an herbicidally effective amount of a pyrrolidone compound of theformula ##STR6## in which X is hydrogen, chlorine or methyl;

Y is hydrogen, chlorine, or bromine;

Z is chlorine or bromine;

R is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine,trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl,trifluoromethylsulfonyl, pentafluoropropionamido, or 3-methylureido;

R₁ is hydrogen, alkyl, chlorine, or trifluoromethyl; and,

R₂ is alkyl or hydrogen; and,

(b) a non-phytotoxic antidotally effective amount of a compound of theformula ##STR7##

The locus where selectivity is desired may include soil, seeds,seedlings, and vegetation.

Preparation

The pyrrolidone compounds of the present invention can be prepared bythe procedures described in U.S. Pat. No. 4,110,105.

The diallyl dichloroacetamide compound of this invention may be preparedaccording to the following procedure. Three and seven-tenths grams (3.7g) (0.025 mole) of dichloroacetyl chloride were dissolved in 100milliliters (ml) of dichloromethane and cooled to 5° C. in an ice bath.Four and nine-tenths g (4.9 g) (0.05 mole) of diallylamine were addedslowly, and the temperature was maintained at about 10° C.

The reaction mixture was stirred at room temperature for four hours,washed twice with water, dried over magnesium sulfate, filtered andstripped. Yield was 4.0 g of diallyl dichloroacetamide. n_(D) ³⁰=1,4990. Structure was confirmed by infrared and nuclear magneticresonance spectroscopy.

Testing

A stock solution of the pyrrolidone was prepared by diluting therequisite amount of the herbicide in water or in an acetone-watersolution. Examples of solution compositions and application rates aresummarized in Table I.

                  TABLE I                                                         ______________________________________                                        Herbicide Stock Solutions                                                              Composition      Application                                                    Herbicide Water   Acetone                                                                              ml/   lb/                                 Herbicide Name                                                                           (mg)*     (ml)    (ml)   flat**                                                                              acre                                ______________________________________                                        1-m-trifluor-                                                                 methylphenyl-3-                                                                          781       100     --           1.25                                chloro-4-chloro                                                               methyl-2-  122        20     20           0.5                                 pyrrolidone                                                                   ______________________________________                                          * The weight is measured in terms of mg of formulated herbicide.              ** The flats measure 5.95 inches by 9.5 inches. Approximately four (4)       mg/flat is equal to one (1) lb/acre.                                     

In each case, the herbicide was applied to the soil after planting seedsand prior to emergence of plants. The herbicide was applied to the soilalone prior to pre-emergence surface application of the antidote orfollowing in-furrow application of the antidote.

Stock solutions of the antidote compound were prepared at the desiredconcentrations by diluting the requisite amount in acetone or in anacetone-water solution. Examples of solution compositions, rates andapplication methods are summarized in Table II.

                  TABLE II                                                        ______________________________________                                        Antidote Stock Solutions                                                      Antidote: Diallyl dichloroacetamide                                           Composition                                                                           Acetone Water   Application                                           Anitdote (mg)                                                                           (ml)      (ml)    ml/flat                                                                             lb/acre                                                                             Method                                ______________________________________                                        95        15        --      0.30  1.00  IF*                                   95        15        --      1.50  5.00  IF                                    60        20        20            1.00  PES**                                 300       20        20            5.00  PES                                   ______________________________________                                         *IF = Infurrow surface application of antidote.                               **PES = Preemergent surface application.                                 

The antidote solutions were applied to the soil either by in-furrowsurface application or by pre-emergence surface application.

For in-furrow application, a one pint (473 cubic centimeter (cc)) sampleof soil containing the previously incorporated herbicide was removed andretained from each planting flat. After leveling and furrowing the soil,seeds of the crop or weed species were planted 1/2 inch deep (1.27centimeter). Each flat was divided in half by a wooden barrier. A stocksolution of the antidote was atomized directly onto the exposed seedsand soil in the open furrow on one side of the barrier. The seeds in theentire flat were then covered with the previously removed soil. Theantidotally untreated sections of flats were compared for observeddifferences which would indicate lateral movement of the antidotethrough the soil.

Control flats contained crops treated with herbicide only. All flatswere placed on greenhouse benches where temperature was maintainedbetween 70° and 90° F. (21.1° to 32.2° C.). The flats were watered bysprinkling as needed to assure good plant growth.

All of the soil used in the tests described herein was loamy sand soiltreated with 50 parts per million (ppm) each of a commercially availablefungicide, N-[(trichloromethyl)-thio]-4-cyclohexene-1,2dicarboximide,and 18-18-18 fertilizer, which contains 18% by weight equivalent each ofnitrogen, phosphorus pentoxide, and potassium oxide.

Injury ratings were taken four weeks after application of the antidote.The effectiveness of the antidote was determined by visual comparison ofcrop injury which occurred in the test flats to that which occurred inthe control flats.

The treated crops initially screened for diminution of herbicidal injurywere milo, wheat, cotton, rice, barley, corn and soybeans. The compoundswere also tested on weed species. The weed species tested includedwatergrass (Echinochloa crusgalli), foxtail (Setaria viridis), wild oat(Avena fatua) and mustard (Brassica spp.)

KEY TO TABLES III AND IV Herbicide1-m-Trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidoneApplication Methods

IF=In-furrow surface application of antidote (soil subsequently treatedwith herbicide only)

PES=Pre-emergence surface application of herbicide or antidote

If no antidote was applied, the word "none" appears in the Antidote Ratecolumn. The results shown on this line are the percent injuriessustained by each of the crops when treated with the herbicide only atthe rate specified.

All rates shown, for both herbicide and antidote, are in pounds peracre.

Injury Ratings

The injury to the crops (Table III) or weeds (Table IV) is shown as apercentage of damage done to the plants as compared to an evaluation ofthe overall undamaged state of the plants. The damage done to the plantsis a function of the number of plants injured and the extent of injuryto each plant. This rating is made four (4) weeks after application ofthe herbicide alone or of the herbicide in combination with theantidote.

An asterisk (*) in Table III indicates that the antidote compound isactive in reducing herbicidal injury to the crop.

Table IV shows that the antidote compounds tested have no effect onweeds, i.e., herbicidal injury to the weeds is sustained even in thepresence of the antidote compound.

                                      TABLE III                                   __________________________________________________________________________    Antidotal Effectiveness                                                       Herbicide    Antidote                                                                           Antidote                                                                           Milo                                                                              Wheat                                                                             Cotton                                                                            Rice                                                                              Barley                                                                            Corn                                                                              Soybean                        Name      Rate                                                                             Rate Method                                                                             % Inj                                                                             % Inj                                                                             % Inj                                                                             % Inj                                                                             % Inj                                                                             % Inj                                                                             % Inj                          __________________________________________________________________________    1-m-trifluoromethyl-                                                                    1.00                                                                             none --       100 50  100 100                                    phenyl-3-chloro-                                                                        1.00                                                                             5.00 IF       100 50  100 100                                    4-chloromethyl-                                                               2-pyrrolidone                                                                           1.25                                                                             none --       100 70  100 100                                              1.25                                                                             5.00 IF       100 70  100 100                                              0.50                                                                             none --   90                   75  65                                      0.50                                                                             5.00 IF   90                  *40  65                                      0.50                                                                             none --   100                 100 100                                      0.50                                                                             5.00 IF   100                 *60 100                                      0.50                                                                             none --                        90                                          0.50                                                                             1.00 IF                       *40                                          0.50                                                                             5.00 IF                       *45                                          0.50                                                                             none --                        55                                          0.50                                                                             1.00 IF                       *25                                          0.50                                                                             5.00 IF                       *25                                          0.50                                                                             none --   75                   70                                          0.50                                                                             1.00 PES  75                   70                                          0.50                                                                             5.00 PES  75                   70                                          0.50                                                                             none --                        65                                          0.50                                                                             1.00 PES                      *30                                          0.50                                                                             2.00 PES                      *35                                          0.50                                                                             5.00 PES                      *35                                          0.50                                                                             none --                        55                                          0.50                                                                             1.00 PES                      *40                                          0.50                                                                             5.00 PES                      *35                                __________________________________________________________________________

                  TABLE IV                                                        ______________________________________                                        Herbicidal Effectiveness                                                                              Anti-                                                                  Anti-  dote                                                                   dote   Meth- Water-                                                                              Fox- Wild Mus-                            Herbicide Rate   Rate   od    grass tail Oat  tard                            ______________________________________                                        1-m-trifluoro-                                                                          0.50   none   --                    100                             methylphenyl-3-                                                                         0.50   5.00   IF                    100                             chloromethyl-2-                                                                         0.50   none   --                    100                             pyrrolidone                                                                             0.50   5.00   IF                    100                                       0.50   none   --    100             100                                       0.50   1.00   IF    100             100                                       0.50   5.00   IF    100             100                                       0.50   none   --    100             100                                       0.50   1.00   IF    100             100                                       0.50   5.00   IF    100             100                                       0.50   none   --          100       100                                       0.50   1.00   PES         100       100                                       0.50   2.00   PES         100       100                                       0.50   5.00   PES         100       100                                       0.50   none   --    100   100  90   100                                       0.50   1.00   PES   100   100  90   100                                       0.50   5.00   PES   100   100  90   100                             ______________________________________                                    

Test Results

The composition of pyrrolidone herbicide and antidote compound waseffective for the reduction of herbicidal injury to corn crops. Use ofthe antidote compound did not result in a reduction of herbicidal injuryto weeds.

Formulations

A formulation is the incorporation of a formulant in a form which isdirectly usable on crops and weeds. As defined herein, a "formulant" isthe material which is to be formulated. The formulant may be either anantidote compound alone or an herbicide and antidote composition. Thepurpose of the formulation is to apply the formulant to the locus whereit is desired to establish herbicidal selectivity by a convenientmethod. The "locus" may include soil, seeds, seedlings and vegetation.

The formulations are commonly dusts, wettable powders, granules,solution or emulsifiable concentrates.

Dusts are free-flowing powder compositions containing the formulantimpregnated on a particulate carrier. The particle size of the carriersis usually in the approximate range of 30 to 50 microns. Examples ofsuitable carriers are talc, bentonite, diatomaceous earth, andpyrophyllite. The composition generally contains up to 50% of formulant.Anti-caking and anti-static agents may also be added. Dusts may beapplied by spraying from boom and hand sprayers on airplanes.

Wettable powders are finely divided compositions comprising aparticulate carrier impregnated with the formulant and additionallycontaining one or more surface active agents. The surface active agentpromotes rapid dispersion of the powder in an aqueous medium to formstable, sprayable suspensions. A wide variety of surface active agentscan be used, for example, long chain fatty alcohols and alkali metalsalts of the sulfated fatty alcohols; salts of sulfonic acid; esters oflong chain fatty acids; and polyhydric alcohols, in which the alcoholgroups are free, omega-substituted polyethylene glycols of relativelylong chain length. A list of surface active agents suitable for use inagriculture formulations can be found in Wade Van Valkenburg, PesticideFormulations (Marcel Dekker, Inc., N.Y., 1973) at pages 79-84.

Granules comprise the formulant impregnated on a particulate inertcarrier having a particle size of about 1 to 2 millimeters (mm) indiameter. The granules can be made by spraying a solution of theformulant in a volatile solvent onto the granular carrier. Examples ofsuitable carriers for the preparation of granules include clay,vermiculite, sawdust, and granular carbon.

Emulsifiable concentrates consist of an oil solution of the formulantplus an emulsifying agent. Prior to use the concentrate is diluted withwater to form a suspended emulsion of oil droplets. The emulsifiers usedare usually a mixture of anionic and nonionic surfactants. Otheradditives, such as suspending agents and thickeners, may be included inthe emulsifiable concentrate.

When the formulant is an antidote and herbicide composition, theproportion of antidote compound to herbicide compound generally rangesfrom approximately 0.001 to 30 parts by weight of the antidote compoundper weight of the herbicide compound.

Formulations generally contain several additives in addition to theformulant and carrier or agent. Among these are inert ingredients,diluent carriers, organic solvents, water, oil and water, water in oilemulsions, carriers of dusts and granules, and surface active wetting,dispersing and emulsifying agents. Fertilizers, e.g., ammonium nitrate,urea and superphosphate, may be included. Aids to rooting and growth,e.g., compost, manure, humus and sand, may also be included.

Alternatively, the antidote compounds and herbicide and antidotecompositions of this invention can be applied to a crop by addition ofthe formulant to irrigation water supplied to the field to be treated.This method of application permits the penetration of the compositionsinto the soil as the water is absorbed.

As another alternative, the formulant can be applied to the soil in theform of a solution in a suitable solvent. Solvents frequently used inthese formulations include kerosene, fuel oil, xylene, petroleumfractions with boiling ranges above xylene and aromatic petroleumfractions rich in methylated naphthalenes. Liquid solutions, like dusts,may be applied by spraying from boom and hand sprayers on airplanes.

What is claimed is:
 1. A composition comprising:(a) an herbicidallyeffective amount of a pyrrolidone compound of the formula ##STR8## inwhich X is hydrogen, chlorine or methyl;Y is hydrogen, chlorine, orbromine; Z is chlorine or bromine; R is hydrogen, alkyl, acetyl,chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano,alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio,trifluoromethylsulfinyl, trifluoromethylsulfonyl,pentafluoropropionamido, or 3-methylureido; R₁ is hydrogen, alkyl,chlorine, or trifluoromethyl; and, R₂ is alkyl or hydrogen; and, (b) anon-phytotoxic antidotally effective amount of a compound of the formula##STR9##
 2. A composition as defined in claim 1 wherein X is hydrogen, Yis chlorine, Z is chlorine, R is m-trifluoromethyl, R₁ is hydrogen, andR₂ is hydrogen.
 3. A method of controlling undesirable vegetation andreducing pyrrolidone-type herbicidal crop injury which comprisesapplying to the locus where control is desired an herbicidally effectiveamount of a composition comprising:(a) an herbicidally effective amountof a pyrrolidone compound of the formula ##STR10## in which X ishydrogen, chlorine or methyl;Y is hydrogen, chlorine, or bromine; Z ischlorine is bromine; R is hydrogen, alkyl, acetyl, chlorine, bromine,fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, trifluoromethylthio,trifluoromethylsulfinyl, trifluoromethylsulfonyl,pentafluoropropionamido, or 3-methylureido; R₁ is hydrogen, alkyl,chlorine, or trifluoromethyl; and, R₂ is alkyl or hydrogen; and, (b) anon-phytotoxic antidotally effective amount of a compound of the formula##STR11##
 4. A method as defined in claim 3 wherein X is hydrogen, Y ischlorine, Z is chlorine, R is m-trifluoromethyl, R₁ is hydrogen, and R₂is hydrogen.